Djokovic, who currently holds all four grand slam titles following his maiden French Open victory earlier this month, will start his tournament defence against Britain’s James Ward on Centre Court.
The Wimbledon championships also represent the third instalment of the 29-year-old top seed’s bid to claim the first calendar slam – all four major tournaments in the same year – since Rod Laver in 1969.
“I’m at the peak of my career at the moment,” said Djokovic.
“I see still lots of room for improvement, things that I can work on. That’s something that encourages me. That’s something that keeps me grounded in a way, gives me more reason to practice.”
Six British men are in action tomorrow, including Kyle Edmund who plays Adrian Mannarino of France, while Laura Robson goes up against fourth seed Angelique Kerber and Naomi Broady plays Elena Vesnina.